Performance and durability of Pt/C cathode catalysts with different kinds of carbons for polymer electrolyte fuel cells characterized by electrochemical and in situ XAFS techniques

The electrochemical activity and durability of Pt nanoparticles on different kinds of carbon supports in oxygen reduction reactions (ORR) were investigated using rotating disc electrodes (RDE) and the membrane electrode assemblies (MEA) of polymer electrolyte fuel cells (PEFC). The mass activity of Pt/C catalysts (ORR activity per 1 mg of Pt) at the RDE decreased, according to the type of carbon support, in the following order; Ketjenblack (KB) > acetylene black (AB) > graphene > multiwall carbon nanotube (MW-CNT) > carbon black (CB), whereas the average size of the Pt nanoparticles and the surface specific activity (ORR activity per electrochemical surface area) did not vary significantly between these carbon supports. These results indicate that the different mass activities of the Pt/C catalysts may originate from the differences in the fraction of Pt on the carbon supports which is available for utilization. The durability of the MEAs of the top two active catalysts Pt/KB and Pt/AB among the five catalysts was examined based on ORR performance, TEM and in situ XAFS. It was found that the performance of the Pt/KB cathode catalyst in PEFC MEA decreased significantly over 500 accelerated durability test (ADT) cycles, whereas the performance of the Pt/AB cathode catalyst in PEFC MEA did not decrease significantly during 500 ADT cycles, it was also found that the Pt/AB possesses 8 times higher durability compared with the Pt/KB. In situ Pt L-III-edge XAFS data in the ADT cycles and stepwise potential operations revealed the different oxidation-reduction behaviors of the Pt nanoparticles on the KB and AB supports. The Pt/KB was oxidized to form surface PtO layers more easily than the Pt/AB in the increasing potential operation from 0.4 V-RHE to 1.4 V-RHE, and the surface PtO layers of the Pt/AB were reduced to the metallic Pt state more readily than those of the Pt/KB in the decreasing potential operation from 1.4 V-RHE to 0.4 V-RHE. The XAFS analysis for the Pt valences and the coordination numbers of Pt-O and Pt-Pt demonstrated that the Pt/AB catalyst is more durable than the Pt/KB catalyst in PEFC MEAs.